EP0490198B1 - Procédé de préparation d'acides 3-aryle acryliques et de leurs dérivés - Google Patents

Procédé de préparation d'acides 3-aryle acryliques et de leurs dérivés Download PDF

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Publication number
EP0490198B1
EP0490198B1 EP91120613A EP91120613A EP0490198B1 EP 0490198 B1 EP0490198 B1 EP 0490198B1 EP 91120613 A EP91120613 A EP 91120613A EP 91120613 A EP91120613 A EP 91120613A EP 0490198 B1 EP0490198 B1 EP 0490198B1
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EP
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Prior art keywords
acid
alkyl
groups
ketene
formula
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EP91120613A
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German (de)
English (en)
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EP0490198A2 (fr
EP0490198A3 (en
Inventor
Michael Dr. Huellmann
Josef Dr. Gnad
Rainer Dr. Becker
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
    • C07C59/40—Unsaturated compounds
    • C07C59/58—Unsaturated compounds containing ether groups, groups, groups, or groups
    • C07C59/64—Unsaturated compounds containing ether groups, groups, groups, or groups containing six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
    • C07C57/30—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms containing six-membered aromatic rings
    • C07C57/42—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms containing six-membered aromatic rings having unsaturation outside the rings
    • C07C57/44—Cinnamic acid
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/46—Preparation of carboxylic acid esters from ketenes or polyketenes

Definitions

  • DE-A 34 37 634 (1) is used in the presence of catalytic amounts of iron and / or zinc salts of mono- or dicarboxylic acids, although an expensive depolymerization step is necessary to form the free cinnamic acids.
  • the yields and the purity of the products obtained are in need of improvement in the process described in (1).
  • 3-arylpropionic acid derivatives III which occur as intermediates in the process according to the invention are known, e.g. 3-methoxy-3-phenylpropionic acid methyl ester and its p-methyl, p-methoxy, p-chloro and p-fluorine derivative from the reference J. Organomet. Chem. 234 (1982), 73-83, (3).
  • the object of the present invention was to provide a production process for the compounds I which is improved with regard to economy, yield and purity of the products.
  • Ar represents a phenyl, biphenylyl or naphthyl radical which is mono- or disubstituted by one to three C1-C4-alkyl groups, C1-C4-alkoxy groups, hydroxyl groups, phenoxy groups, amino groups which are substituted by C1-C4-alkyl groups can be halogen atoms, nitro groups or a methylenedioxy group, where the substituents can be the same or different.
  • Ar examples include: Phenyl, o-, m- or p-tolyl, o-, m- or p-ethylphenyl, o-, m- or p-propylphenyl, m- or p-cumyl, o-, m- or p-butylphenyl, m- or p-iso-butylphenyl, m- or p-sec-butylphenyl, m- or p-tert-butylphenyl, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-dimethylphenyl, Mesityl, o-, m- or p-methoxyphenyl, o-, m- or p-ethoxyphenyl, o-, m- or p-propoxyphenyl, m- or p-iso-propoxyphenyl, o-, m- or p-but
  • C1-C4 alkoxyphenyl radicals are particularly preferred, in particular if the alkoxy radical is in the p-position on the phenyl nucleus.
  • R1 denotes hydrogen, an alkali metal, especially sodium or potassium, an alkaline earth metal, e.g. Calcium or magnesium, or ammonium, the compounds I are the free 3-arylacrylic acids or their salts.
  • R1 is a C1 to C20 alkyl group
  • 3-arylacrylic acid alkyl esters are present. Of these, hydrogen and in particular C1 to C20 alkyl groups are preferred.
  • straight-chain or branched C1- to C20-alkyl groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 2nd -Ethylhexyl, n-nonyl, iso-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, iso-tridecyl, n-tetradecyl, n-hexadecyl, n-octadecyl and n-eicosyl.
  • straight-chain or branched C6 to C16 alkyl groups in particular straight-chain or branched C8 to C12 alxyl groups, are preferred.
  • a dialkylacetal of an aromatic aldehyde II in which R2 for C1- to C4-alkyl is used as acetal radicals, e.g. Methyl, ethyl, n-propyl, iso-propyl, n-butyl, 1,2-ethylene or 1,3-propylene can occur, with methyl and ethyl being preferred, with ketene usually at a temperature of from -20 to 80 ° C , in particular -10 to 50 ° C, implemented. It is expedient to use 0.8 to 1.2 mol, preferably 0.9 to 1.1 mol, in particular 0.94 to 1.06 mol of ketene per mol of II.
  • the reaction is preferably carried out without solvent, but can also be carried out in an inert proton-free organic solvent.
  • solvents include hydrocarbons, e.g. Pentane, hexane, heptane, octane, cyclohexane, toluene, xylene or mixtures thereof, or ether, e.g. Diethyl ether, methyl tert-butyl ether or tetrahydrofuran, or mixtures thereof.
  • the reaction of II with ketene is carried out in the presence of catalytic amounts of a protonic acid, for example sulfuric acid, hydrochloric acid, acetic acid, formic acid or p-toluenesulfonic acid, or a Lewis acid, for example a boron trihalide dialkyl etherate, such as boron trifluoride dimethyl etherate or boron trifluoride diethyl etherate, a titanium tetraalkoxy compound or a zinc carboxylate.
  • Catalytic amounts are usually understood to mean amounts of 0.001 to 1 mol% per mole II for protonic acids, and amounts of 0.1 to 10 mol% per mole II usually for Lewis acids.
  • Intermediate III can generally be easily isolated in pure form, for example by distillation in vacuo. In a preferred embodiment of the process according to the invention, however, isolation of intermediate III is dispensed with and the further reaction of the second reaction stage is carried out with the crude product of the first reaction stage.
  • intermediate III is in the presence of acid, usually a protonic acid, e.g. Sulfuric acid hydrochloric acid, acetic acid, formic acid or p-toluenesulfonic acid, or base, e.g. Alkali or alkaline earth metal hydroxide such as sodium hydroxide, potassium hydroxide or calcium hydroxide or alkali or alkaline earth metal alcoholate such as sodium methylate, sodium ethylate or potassium tert-butoxide.
  • acid usually a protonic acid, e.g. Sulfuric acid hydrochloric acid, acetic acid, formic acid or p-toluenesulfonic acid
  • base e.g. Alkali or alkaline earth metal hydroxide such as sodium hydroxide, potassium hydroxide or calcium hydroxide or alkali or alkaline earth metal alcoholate such as sodium methylate, sodium ethylate or potassium tert-butoxide.
  • Customary catalytic amounts thereof are normally sufficient for such hydrolysis and elimination reactions; However, if, for example, the alkali or alkaline earth metal salt of 3-arylacrylic acid I is to be obtained, stoichiometric amounts of the corresponding base are necessary.
  • 3-arylacrylic acid C1 to C20 alkyl esters are to be prepared as 3-arylacrylic acid derivatives I, a C1 to C2anol alkanol must also be used.
  • This reaction is a transesterification reaction, ie an exchange of the alkyl group R2 for an alkyl group R1, with the simultaneous elimination of a second alcohol molecule R2-OH.
  • the C1 to C20 alkanol is used in an equimolar amount or preferably in excess, about 1.1 to 10 mol per mol III, in particular 2 to 10 mol per mol III.
  • the Ar group carries substituents which have been protonated by an acid treatment during the process according to the invention or have formed an adduct with a Lewis acid, or substituents which have been anionized by a base treatment during the process according to the invention, these substituents can easily be treated with an appropriate amount of a suitable base or acid can be returned to the original form.
  • the process according to the invention opens up a simple and economical way of producing 3-arylacrylic acids and their derivatives I, especially since the starting compound II is easily accessible by electrochemical oxidation of the methyl group of the corresponding methyl aromatics.
  • the aromatic aldehydes used as starting compounds of the process known from (1) can only be obtained by complex synthetic processes, for example by the toxicologically questionable chromic acid oxidation of methyl aromatics, for example toluene derivatives.
  • the process according to the invention provides the compounds I in good yields and free of large amounts of disruptive by-products, so that subsequent cleaning operations are unproblematic. Excellent space-time yields result in particular from a solvent-free driving style.
  • This liquid was mixed with 40 g of a 30% by weight methanolic sodium methylate solution, a pH of about 10 being established and the violet changing to a yellow-brown color.
  • methanolic sodium methylate solution a 30% by weight
  • the violet changing to a yellow-brown color.
  • the mixture was slowly heated to 150 to 180 ° C., 151 g of a liquid consisting mainly of methanol being distilled off over the course of about 1 hour.
  • Excess 2-ethylhexanol was distilled off and the residue obtained was purified by distillation in an oil pump vacuum at about 1 mbar. This gave 436 g of the title compound with a boiling point of 165 ° C. at 0.3 mbar, corresponding to a yield of 75%, based on the p-methoxybenzaldehyde dimethyl acetal used.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Claims (3)

  1. Procédé de préparation d'acides 3-arylacryliques et leurs dérivés de formule générale I
    Figure imgb0011
     dans laquelle
    Ar est mis pour un reste aryle qui peut porter additionnellement des substituants qui ne réagissent pas avec une cétine, et également sont stables aux acides et aux bases dans les conditions de la réaction décrite ci-dessous
    R¹ signifie hydrogène, un métal alcalin, un métal alcalino-tèrreux, ammonium ou un groupe alkyle en C1 à C20
    caractérisé par le fait que, dans une première étape de réaction, on fait réagir un dialkylacétal d'un aldéhyde aromatique de formule II
    Figure imgb0012
     dans laquelle R² est mis pour alkyle en C1 à C4 avec une cétine de formule CH₂ = C = O en présence de quantités catalytiques d'un acide à protons ou un acide de Lewis pour aboutir à un dérivé d'acide 3-arylpropionique de formule générale III
    Figure imgb0013
     et dans une deuxième étape de réaction on fait réagir ce produit intermédiaire III en présence d'acide ou de base et éventuellement, dans le cas où R² représente un groupe alkyle en C1 à C20, avec un alcanol en C1 à C20 pour aboutir au produit final I.
  2. Procédé selon la revendication 1, caractérisé par le fait qu'il est utilisé à la préparation d'acides 3-arylacryliques et leurs dérivés, dans lesquels
    Ar est mis pour un reste phényle, biphénylyle ou naphtyle, qui peut être substitué par un à trois groupes alkyle en C1-C4, groupes alcoxy en C1-C4, groupes hydroxyle, groupes phénoxy, groupes amino, qui peuvent être mono- ou disubstitués par des groupes alkyle en C1-C4, des atomes halogène, des groupes nitro ou un groupe méthylènedioxy, les substituants pouvant être identiques ou différents.
  3. Procédé selon la revendication 1 ou 2, caractérisé par le fait qu'on l'effectue sans isolement du produit intermédiaire III.
EP91120613A 1990-12-13 1991-11-29 Procédé de préparation d'acides 3-aryle acryliques et de leurs dérivés Expired - Lifetime EP0490198B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4039782A DE4039782A1 (de) 1990-12-13 1990-12-13 Verfahren zur herstellung von 3-arylacrylsaeuren und ihren derivaten
DE4039782 1990-12-13

Publications (3)

Publication Number Publication Date
EP0490198A2 EP0490198A2 (fr) 1992-06-17
EP0490198A3 EP0490198A3 (en) 1993-05-12
EP0490198B1 true EP0490198B1 (fr) 1996-02-28

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Family Applications (1)

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EP91120613A Expired - Lifetime EP0490198B1 (fr) 1990-12-13 1991-11-29 Procédé de préparation d'acides 3-aryle acryliques et de leurs dérivés

Country Status (3)

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US (1) US5359122A (fr)
EP (1) EP0490198B1 (fr)
DE (2) DE4039782A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DK0909751T3 (da) * 1997-10-16 2002-05-13 Sankyo Co Fremgangsmåde til fremstilling af kanelsyreestere
DE10044381A1 (de) 2000-09-08 2002-04-04 Haarmann & Reimer Gmbh Zimtsäureester

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE626622A (fr) * 1961-12-29
DE3437634A1 (de) * 1984-10-13 1986-04-17 Bayer Ag Verfahren zur herstellung von gegebenenfalls substituierter zimtsaeure in gegenwart eines katalysators
US4785133A (en) * 1987-10-05 1988-11-15 Eastman Kodak Company Process for the preparation of alkyl 3-alkoxypropionates
US4827021A (en) * 1988-03-07 1989-05-02 Eastman Kodak Company Process for the preparation of alkyl 3-alkoxypropionates

Also Published As

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EP0490198A2 (fr) 1992-06-17
DE59107467D1 (de) 1996-04-04
EP0490198A3 (en) 1993-05-12
US5359122A (en) 1994-10-25
DE4039782A1 (de) 1992-06-17

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